Optically active copper catalyst composition

ABSTRACT

There is provided an optically active copper catalyst composition comprising 
 
(a) an optically active salicylideneaminoalcohol represented by the formula (1):  
                 
 
wherein R 1  and R 2  are the same or different, and independently represent a substituted or unsubstituted lower alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group; 
 
X 1  and X 2  are the same or different, and independently represent a hydrogen atom, a lower alkoxy group, a nitro group, a lower alkoxycarbonyl group, a cyano group or a halogen atom; and * represents an asymmetric center, provided that both of X 1  and X 2  don&#39;t represent hydrogen atoms, 
(b) a monovalent or divalent copper compound, and (c-1) a lithium compound or (c-2) a compound selected from aluminum compounds having Lewis acidity, titanium compounds having Lewis acidity, boron compounds having Lewis acidity, zirconium compounds having Lewis acidity and hafnium compounds having Lewis acidity; and a process for producing an optically active cyclopropane compound by using the same.

TECHNICAL FIELD

The present invention relates to a novel optically active coppercatalyst composition and process for production of a cyclopropanecompound using the same.

BACKGROUND ART

Optically active cyclopropane compounds are important compounds assynthesis intermediates of pharmaceuticals and/or agriculturalchemicals. For example,(+)-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylic acid,which is a representative optically active cyclopropane compound, hasbeen known to be useful for an acidic moiety of a synthesized pyrethroidtype insecticide. As a method for producing the optically activecyclopropane compounds, for example, method for reacting2,5-dimethyl-2,4-hexadiene with a diazoacetic acid ester in the presenceof an optically active salicylideneaminoalcohol copper complex catalystis known (e.g. JP 59-225194 A), and improving the catalyst activity bymodifying the substituents of salicylideneaminoalcohol has been tried(e.g. JP 2001-278853 A).

DISCLOSURE OF THE INVENTION

According to the present invention, a diazotization reaction catalystwhich exhibits good activity is obtained, and an optically activecyclopropane compound can be produced easily by using the catalyst.

That is, the present invention provides,

1. an optically active copper catalyst composition (hereinafter, simplypreferred to as the copper catalyst composition of the presentinvention) comprising

(a) an optically active salicylideneaminoalcohol represented by theformula (1):

wherein R¹ and R² are the same or different, and independently representa substituted or unsubstituted lower alkyl group, a substituted orunsubstituted aralkyl group, or a substituted or unsubstituted arylgroup;X¹ and X² are the same or different, and independently represent ahydrogen atom, a lower alkoxy group, a nitro group, a loweralkoxycarbonyl group, a cyano group or a halogen atom; and * representsan asymmetric center, provided that both of X¹ and X² don't representhydrogen atoms (hereinafter, simply preferred to as the optically activesalicylideneaminoalcohol (1)),(b) a monovalent or divalent copper compound, and(c-1) a lithium compound or(c-2) a compound selected from aluminum compounds having Lewis acidity,titanium compounds having Lewis acidity, boron compounds having Lewisacidity, zirconium compounds having Lewis acidity and hafnium compoundshaving Lewis acidity; and2. A process for producing an optically active cyclopropane compoundrepresented by the formula (4):

wherein R³, R⁴, R⁵ and R⁶ are the same or different, and independentlyrepresent a hydrogen atom, an alkyl group which may be substituted withone or more halogen atom, an alkenyl group which may be substituted withone or more halogen atom, an aryl group or an aralkyl group; providedthat, when R³ and R⁵ are the same, R³ and R⁴ are different from eachother; and R⁷ represents a C1-6 alkyl group (hereinafter, simplypreferred to as the optically active cyclopropane compound (4)), whichcomprises reacting a prochiral olefin represented by the formula (2):

wherein R³, R⁴, R⁵ and R⁶ are as defined above (hereinafter, simplypreferred to as the olefin (2)), with a diazoacetic acid esterrepresented by the formula (3):N₂CHCO₂R⁷  (3)wherein R⁷ is as described above (hereinafter, simply preferred to asthe diazoacetic acid ester (3)), in the presence of the above-mentionedoptically active copper catalyst composition.

BEST MODE FOR CARRYING OUT THE PRESENT INVENTION

The copper catalyst composition of the present invention will beillustrated below.

In the optically active salicylideneaminoalcohol (1), the unsubstitutedlower alkyl group represented by R¹ or R² include, for example, a C1-4alkyl group such as a methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl and tert-butyl group. Examples of the substituent of thesubstituted lower alkyl group include, for example, a C1-4 lower alkoxygroup such as a methoxy, ethoxy, propoxy and butoxy group.

Examples of the unsubstituted aryl group include, for example, a phenylgroup. Examples of the substituent of the substituted aryl groupinclude, for example, a substituent selected from a lower alkyl group(for example, C1-4 alkyl group like the above), a lower alkoxy group(for example, C1-4 alkoxy group like the above) and the like.

Specific examples of the substituted aryl group include, for example, a2-methoxyphenyl and a 2-n-butoxy-5-tert-butylphenyl group.

Examples of the unsubstituted aralkyl group include, for example, loweralkyl groups substituted with a unsubstituted aryl group (for example, aphenyl group), and examples of the substituted aralkyl group includelower alkyl groups substituted with the substituted aryl group like theabove (for example, an aryl group substituted with a C1-4 alkyl group ora C1-4 alkoxy group). Examples of the lower alkyl group of the loweralkyl group substituted with the unsubstituted or substituted aryl groupinclude, for example, a C1-4 alkyl group like the above. Specificexamples of them include, for example, a benzyl and 2-methoxybenzylgroup.

X¹ and X² in the formula of the above-mentioned optically activesalicylidenaminoalcohol (1) will be illustrated below.

Examples of the lower alkoxy group represented by X¹ and X² include, forexample, a lower alkoxy group having 1 to 4 carbon atoms such as amethoxy, ethoxy, propoxy and butoxy group.

Examples of the lower alkoxy group of the lower alkoxycarbonyl grouprepresented by X¹ and X² include the above-mentioned C1-4 alkoxy group,and specific examples of the lower alkoxycarbonyl group include, forexample, a methoxycarbonyl, ethoxycarbonyl, propoxycarboyl andbutoxycarbonyl group.

Examples of the halogen atom represented by X¹ and X² include, forexample, a fluorine, chlorine and bromine atom.

Examples of the optically active salicylideneaminoalcohol (1) include,for example,(R)-N-(3-nitrosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(5-nitrosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(3,5-dinitrosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)—N-(3-chlorosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(5-chlorosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(3,5-dichlorosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(3-fluorosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(5-fluorosalicylidene)-2-amino-1,1-diphenyl-1-propanol,

(R)-N-(3-bromosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(5-bromosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(3-methoxycarbonylsalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(5-methoxycarbonylsalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(3-cyanosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(5-cyanosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(3-fluoro-5-nitrosalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)-N-(3-methoxysalicylidene)-2-amino-1,1-diphenyl-1-propanol,(R)—N-(5-methoxysalicylidene)-2-amino-1,1-diphenyl-1-propanol,

(R)-N-(3-nitrosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(3,5-dinitrosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(3-chlorosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(5-chlorosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(3,5-dichlorosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(3-fluorosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(5-fluorosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,

(R)-N-(3-bromosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(5-bromosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(3-methoxycarbonylsalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(5-methoxycarbonylsalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(3-cyanosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(5-cyanosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(3-fluoro-5-nitrosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(3-methoxysalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,(R)-N-(5-methoxysalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,

(R)-N-(3-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(3,5-dinitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(3-chlorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(5-chlorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(3,5-dichlorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(3-fluorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(5-fluorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,

(R)-N-(3-bromosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(5-bromosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(3-methoxycarbonylsalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(5-methoxycarbonylsalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(3-cyanosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(5-cyanosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(3-fluoro-5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(3-methoxysalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,(R)-N-(5-methoxysalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,

(R)-N-(3-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(3,5-dinitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(3-chlorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(5-chlorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(3,5-dichlorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(3-fluorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(5-fluorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,

(R)-N-(3-bromosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(5-bromosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(3-methoxycarbonylsalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(5-methoxycarbonylsalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(3-cyanosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(5-cyanosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(3-fluoro-5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(3-methoxysalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,(R)-N-(5-methoxysalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-3-phenyl-1-propanol,and these compounds in which the configuration (R) is changed to (S).

The optically active salicylideneaminoalcohol has R— and S-isomer, andin the present invention, either any one of the isomers may be used.

The optically active salicylideneaminoalcohol (1) can be producedaccording to a method of reaction of a corresponding aminoalcohol and acorresponding salicylaldehyde (described in e.g. JP-2001-278853 A andthe corresponding U.S. patent application Numbers 2001037036 and2002004618, U.S. Pat. Nos. 6,469,198 and 6,670,500).

Examples of the monovalent or divalent copper compound include, forexample, a C2-15 copper organic carboxylate such as copper(I) acetate,copper (II) acetate, copper(II) naphthenate and copper(II) octanoate,and a monovalent or divalent copper salt or copper complex such ascopper(II) acetylacetonate, copper(I) chloride, copper(II) chloride,copper(I) bromide, copper(II) bromide, copper(II) methanesulfonate,copper(I) trifluoromethanesulfonate, copper(II)trifluoromethanesulfonate, copper(II) carbonate and copper(II)hydroxide. The copper compound may be used alone or two or more thereofmay be combined to use.

Examples of the lithium compound include, for example, a lithium saltrepresented by lithium halide such as lithium chloride, lithium bromide,lithium iodide and lithium fluoride, alkoxylithium such asmethoxylithium, ethoxylithium, propoxylithium and butoxylithium, lithiumhydroxide or a mixture thereof.

Aluminum compounds having Lewis acidity, titanium compounds having Lewisacidity, boron compounds having Lewis acidity, zirconium compoundshaving Lewis acidity and hafnium compounds having Lewis acidity will beillustrated below.

Examples of aluminum compounds having Lewis acidity include, forexample, trihaloaluminum such as aluminum trichloride, trialkylaluminumsuch as trimethylaluminum, triethylaluminum and triisobutylaluminum,trialkoxyaluminum such as triethoxyaluminum, triaryloxyaluminum such astriphenoxyaluminum, and tris(pentafluorophenyl)aluminum.

Examples of titanium compounds having Lewis acidity include, forexample, tetrahalotitanium such as titanium tetrachloride, andtetraalkoxytitanium such as tetraisopropoxytitanium andtetra(n-butoxy)titanium.

Examples of boron compounds having Lewis acidity include, for example,boron trifluoride diethyl etherate, triethylborane, triphenylborane, andtris(pentafluorophenyl)borane.

Examples of zirconium compounds having Lewis acidity include, forexample, zirconium halide (IV) or the complex such as zirconiumtetrachloride and zirconium tetrachloride tetrahydrofuran complex, andtetraalkoxyzirconium such as tetra(n-butoxy)zirconium.

Examples of hafnium compounds having Lewis acidity include, for example,hafnium halide (IV) or the complex such as hafnium tetrachloride andhafnium tetrachloride tetrahydrofuran complex.

Triethoxylaluminum, tris(pentafluorophenyl)aluminum,tetraisopropoxytitanium, and tris(pentafluorophenyl)borane arepreferable. The compound having Lewis acidity may be used alone or twoor more thereof may be combined to use.

The optically active copper catalyst composition of the presentinvention is produced by contacting the optically activesalicylideneaminoalcohol (1), the monovalent or divalent copper compoundand the above-mentioned c-1) the lithium compound or the above-mentionedcompound selected from c-2) usually in an organic solvent. The amount ofthe optically active salicylideneaminoalcohol (1) used is usually about0.5 to 2 moles per 1 mole of the monovalent or divalent copper compoundand the amount of the above-mentioned c-1) the lithium compound or theabove-mentioned compound selected from c-2) used is usually about 0.3 to5 moles per 1 mole of the monovalent or divalent copper compound.

The solvent may be a solvent which can dissolved a certain amount of theoptically active copper complex of the present invention, and examplesof the solvent include, for example, aromatic hydrocarbon solvents suchas toluene and xylene; aliphatic hydrocarbon solvents such as hexane,cyclohexane and heptane; halogenated hydrocarbon solvents such aschloroform, dichloroethane and chlorobutane; and ester solvents such asethyl acetate and ethyl propionate. The solvent may be used alone or inthe form of a mixture.

The temperature of contacting the optically activesalicylideneaminoalcohol (1), the monovalent or divalent copper compoundand the above-mentioned c-1) the lithium compound or the above-mentionedcompound selected from c-2) is usually 0° C. to boiling point of thesolvent.

Contacting the optically active salicylideneaminoalcohol (1), themonovalent or divalent copper compound and the above-mentioned c-1) thelithium compound or the above-mentioned compound selected from c-2) maybe carried out by mixing three components in the organic solvent, andthe mixing order is not particularly limited. After isolating thecomplex obtained by contacting the optically activesalicylideneaminoalcohol (1) and the monovalent or divalent coppercompound, the complex may be contacted the above-mentioned c-1) thelithium compound or the above-mentioned compound selected from c-2).Contacting the optically active salicylideneaminoalcohol (1) and themonovalent or divalent copper compound may be carried out in thepresence of a base such as sodium methylate.

A solution or slurry containing the optically active copper catalystcomposition is usually obtained by contacting the optically activesalicylideneaminoalcohol (1), the monovalent or divalent copper compoundand the Lewis acid in the organic solvent, and the optically activecopper catalyst composition can be isolated by concentrating orfiltering the solution or slurry. The solution or slurry containing theoptically active copper catalyst composition may be used as it is forthe cyclopropanation reaction described below.

Next, the following description will illustrate the process forproducing an optically active cyclopropane compound represented by theformula (4) (hereinafter, simply preferred to as the optically activecyclopropane compound (4)), which comprises reacting the prochiralolefin represented by the formula (2) (hereinafter, simply preferred toas the olefin (2)) with the diazoacetic acid ester represented by theformula (3) (hereinafter, simply preferred to as the diazoacetic acidester (3)) in the presence of the optically active copper catalystcomposition obtained above.

In the formula of the above-mentioned olefin (2), examples of the alkylgroup which may be substituted with one or more halogen atoms include,for example, C1-6 alkyl group such as a methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, n-pentyl, and hexyl group, and these alkylgroups whose one or more hydrogen atoms are substituted with theabove-mentioned halogen atoms such as a chloromethyl, fluoromethyl,trifluoromethyl, and chloroethyl group. Examples of the alkenyl groupwhich may be substituted with one or more halogen atoms include a C2-6alkenyl group such as a vinyl, 1-propenyl, 2-propenyl,2-methyl-1-propenyl, 1-butenyl, 2-butenyl and 3-butenyl group, and thesealkenyl groups whose one or more hydrogen atoms are substituted with theabove-mentioned halogen atoms such as a 1-chloro-2-propenyl group. Asthe aryl and aralkyl group, there are, for example, the same groups asR1 and R2 exemplified above.

Examples of the olefin (2) include, for example, propene, 1-butene,isobutylene, 1-pentene, 1-hexene, 1-octene, 4-chloro-1-butene,2-pentene, 2-heptene, 2-methyl-2-butene, 2,5-dimethyl-2,4-hexadiene,2-chloro-5-methyl-2,4-hexadiene, 2-fluoro-5-methyl-2,4-hexadiene,1,1,1-trifluoro-5-methyl-2,4-hexadiene,2-methoxycarbonyl-5-methyl-2,4-hexadiene,1,1-difluoro-4-methyl-1,3-pentadiene,1,1-dichloro-4-methyl-1,3-pantadiene,1,1-dibromo-4-methyl-1,3-pentadiene,1-chloro-1-fluoro-4-methyl-1,3-pentadiene,1-fluoro-1-bromo-4-methyl-1,3-pentadiene, 2-methyl-2,4-hexadiene,1-fluro-1,1-dichloro-4-methyl-2-pentene,1,1,1-trichloro-4-methyl-3-pentene, 1,1,1-tribromo-4-methyl-3-pentene,2,3-dimethyl-2-pentene, 2-methyl-3-phenyl-2-butene,2-bromo-2,5-dimethyl-4-hexene, 2-chloro-2,5-dimethyl-4-hexane, and2,5-dimethyl-6-chloro-2,4-hexadiene.

Examples of C1-6 alkyl group in the formula of the above-mentioneddiazoacetic acid ester (3) include, for example, a C1-6 alkyl group suchas a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl andhexyl group.

Examples of the diazoacetic acid ester (3) include, for example, methyldiazoacetate, ethyl diazoacetate, n-propyl diazoacetate, isopropyldiazoacetate, n-butyl diazoacetate, isobutyl diazoacetate and tert-butyldiazoacetate.

The amount of the olefin (2) to be used is usually 1 mole or more,preferably 1.2 moles or more relative to 1 mole of the diazoacetic acidester (3). There is no specific upper limit and when the olefin (2) is aliquid, large excess thereof can be used also to serve as the solvent.

As the optically active copper complex composition, the eithercomposition having ligand of (R)-isomer or (S)-isomer may be used asdescribed above and a mixture thereof in which one of them exists inexcess than the other may be used. The amount of the optically activecopper complex to be used is usually about 0.0001 to 0.05 mole,preferably about 0.0005 to 0.01 mole in terms of the copper metalrelative to 1 mole of the diazoacetic acid ester (3).

The reaction of the olefin (2) and the diazoacetic acid ester (3) isusually carried out by mixing three components, the optically activecopper catalyst composition, the olefin (2), and the diazoacetic acidester (3), in an atmosphere of an inert gas such as argon gas ornitrogen gas. The mixing order is not particularly limited. Usually, thediazoacetic acid ester (3) is added to a mixture of the optically activecopper catalyst composition and the olefin (2). When the divalent coppercompound is used for preparing the optically active copper catalystcomposition, the reaction may be carried out in the presence of areducing agent such as phenylhydrazine.

The reaction of the olefin (2) and diazoacetic acid ester (3) is usuallycarried out in the presence of a solvent. Examples of the solventinclude, for example, halogenated hydrocarbon solvent such asdichloromethane, dichloromethane, chloroform and carbon tetrachloride;aliphatic hydrocarbon solvent such as hexane, heptane and cyclohexane;aromatic hydrocarbon solvent such as benzene, toluene and xylene; andester solvent such as ethyl acetate. The solvent can be used alone or inthe form of a mixture. Although the amount of the solvent to be used isnot particularly limited, in view of the volume efficiency and theproperties of the reaction mixture, the amount of the solvent to be usedis usually about 2 to 30 parts by weight, preferably 5 to 20 parts byweight relative to 1 part by weight of the diazoacetic acid ester (3).The solvent can be mixed previously with the olefin (2), the diazoaceticacid ester (3), and/or the optically active copper catalyst composition.Alternatively, as described above, when the olefin (2) is a liquid, theolefin (2) can also be used as the solvent.

Since the copper catalyst composition of the present invention has asuperior catalytic activity at low temperature, the reaction can becarried out at lower reaction temperature than ever before. The reactiontemperature is usually about −50 to 50° C., preferably −20 to 30° C.

After completion of the reaction, the optically active cyclopropanecompound (4) can be isolated by, for example, concentrating the reactionmixture. The isolated optically active cyclopropane compound (4) canfurther be purified by a conventional purification means such asdistillation, column chromatography, and the like.

Examples of the optically active cyclopropane compound (4) include, forexample, optically active methyl 2-methylcyclopropanecarboxylate,optically active methyl 2,2-dimethylcyclopropanecarboxylate, opticallyactive methyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate, opticallyactive methyl2,2-dimethyl-3-(2,2-dichloro-1-ethenyl)cyclopropanecarboxylate,optically active methyl2,2-dimethyl-3-(2,2,2-trichloroethyl)cyclopropanecarboxylate, opticallyactive methyl2,2-dimethyl-3-(2,2,2-tribromoethyl)cyclopropanecarboxylate, opticallyactive methyl2,2-dimethyl-3-(2,2-dibromo-1-ethenyl)cyclopropanecarboxylate, opticallyactive methyl2,2-dimethyl-3-(2,2-difluoro-1-ethenyl)cyclopropanecarboxylate,optically active methyl2,2-dimethyl-3-(2-fluoro-2-chloro-1-ethenyl)cyclopropanecarboxylate,optically active methyl2,2-dimethyl-3-(2-fluoro-2-bromo-1-ethenyl)cyclopropanecarboxylate,optically active methyl2,2-dimethyl-3-(2-fluoro-1-propenyl)cyclopropanecarboxylate, opticallyactive methyl2,2-dimethyl-3-(2-chloro-1-propenyl)cyclopropanecarboxylate, opticallyactive methyl2,2-dimethyl-3-(2-chloro-2,2,2-trifluoromethylethenyl)cyclopropanecarboxylate,optically active methyl2,2-dimethyl-3-(2-methoxycarbonyl-1-propenyl)cyclopropanecarboxylate,optically active methyl2,2-dimethyl-3-(2-chloro-2-methylpropyl)cyclopropanecarboxylate,optically active methyl2,2-dimethyl-3-(2-bromo-2-methylpropyl)cyclopropanecarboxylate, andoptically active methyl2,2-dimethyl-3-(1-propenyl)cyclopropanecarboxylate; and compoundswherein the above methyl ester moieties are replaced with ethyl,n-propyl, isopropyl, isobutyl and tert-butyl ester moieties.

The optically active cyclopropane compound (4) can be converted into anoptically active cyclopropanecarboxylic acid in which R⁷ is a hydrogenatom by hydrolysis according to a known hydrolysis method.

EXAMPLES

The present invention will be further illustrated in more detail byExamples. The present invention is not limited to these Examples. Theyield of the optically active cyclopropane compound, thetrans-isomer/cis-isomer ratio and the residual ratio of diazoacetic acidester were calculated from results of gas chromatography.

The optically purity of the optically active cyclopropane compound wascalculated from results of liquid chromatography analysis. Atrans-isomer means the compound having the ester group at 1-position andthe 2-methyl-1-propenyl group at 3-position on the opposite side withrespect to the cyclopropane ring plane and a cis-isomer means thecompound having the ester group at 1-position and the2-methyl-1-propenyl group at 3-position on the same side with respect tothe cyclopropane ring plane.

Example 1

To a 50 mL Schlenk tube purged with nitrogen, 8.73 mg of(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,4.0 mg of copper (II) acetate monohydrate and 5 mL of ethyl acetate wereadded and mixed with stirring at an inner temperature of 50° C. for 30minutes. 5.68 mg of tetraisopropoxytitanium was added to this solution.The resulting solution was stirred at room temperature for 10 minutes toeffect reaction and the optically active copper catalyst composition wasprepared. After adding 4 mg of phenylhydrazine to this solutioncontaining the optically active copper catalyst composition, 7.8 g of2,5-dimethyl-2,4-hexadiene was added thereto and the inner temperaturewas adjusted to 20° C. 5 mL of the ethyl acetate solution containing1.14 g of ethyl diazoacetate was added dropwise thereto over 2 hours.After adding dropwise, the resulting mixture was stirred at the sametemperature for 30 minutes to effect reaction and the reaction solutioncontaining optically active ethyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate wasobtained. The yield of optically active ethyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was 85%(based on ethyl diazoacetate), the trans-isomer/cis-isomer ratio=58/42,and the residual ratio of ethyl diazoacetate was 0.1%. Also, opticalpurity of the trans-isomer was 76% e.e. and that of the cis-isomer was70% e.e.

Comparative Example 1

According to the same manner as that described in Example 1, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 58% and the trans-isomer/cis-isomerratio=58/42 except that tetraisopropoxytitanium was not used. Theresidual ratio of ethyl diazoacetate was 20%. Also, optical purity ofthe trans-isomer was 75% e.e. and that of the cis-isomer was 70% e.e.

Example 2

According to the same manner as that described in Example 1, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 61% and the trans-isomer/cis-isomerratio=57/4.3 except that ethyl diazoacetate was added dropwise at 0° C.The residual ratio of ethyl diazoacetate was 3%. Optical purity of thetrans-isomer was 84% e.e. and that of the cis-isomer was 78% e.e.

Comparative Example 2

According to the same manner as that described in Example 2, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 35% and the trans-isomer/cis-isomerratio=57/43 except that tetraisopropoxytitanium was not used. Theresidual ratio of ethyl diazoacetate was 47%. Optical purity of thetrans-isomer was 83% e.e. and that of the cis-isomer was 78% e.e.

Example 3

According to the same manner as that described in Example 1, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 92% and the trans-isomer/cis-isomerratio=58/42 except that 3.57 mg of triethoxyaluminium was used in placeof 5.68 mg of tetraisopropoxytitanium. The residual ratio of ethyldiazoacetate was 0.1%. Optical purity of the trans-isomer was 77% e.e.and that of the cis-isomer was 71% e.e.

Example 4

According to the same manner as that described in Example 3, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 70% and the trans-isomer/cis-isomerratio=57/43 except that ethyl diazoacetate was added dropwise at 0° C.The residual ratio of ethyl diazoacetate was 5%. Optical purity of thetrans-isomer was 84% e.e. and that of the cis-isomer was 78% e.e.

Example 5

According to the same manner as that described in Example 1, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 65% and the trans-isomer/cis-isomerratio=58/42 except that 7.55 mg of zirconium tetrachloridetetrahydofuran complex was used in place of 5.68 mg oftetraisopropoxytitanium. The residual ratio of ethyl diazoacetate was0.1%. Optical purity of the trans-isomer was 71% e.e. and that of thecis-isomer was 61% e.e.

Example 6

According to the same manner as that described in Example 1, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 84% and the trans-isomer/cis-isomerratio=58/42 except that 9.29 mg of hafnium tetrachloride tetrahydofurancomplex was used in place of 5.68 mg of tetraisopropoxytitanium. Theresidual ratio of ethyl diazoacetate was 0.1%. Optical purity of thetrans-isomer was 76% e.e. and that of the cis-isomer was 71% e.e.

Example 7

According to the same manner as that described in Example 1, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 96% and the trans-isomer/cis-isomerratio=58/42 except that 10.24 mg of tris(pentafluorophenyl)borane wasused in place of 5.68 mg of tetraisopropoxytitanium. The residual ratioof ethyl diazoacetate was 0.1%. Optical purity of the trans-isomer was77% e.e. and that of the cis-isomer was 71% e.e.

Reference Example 1

In a 200 mL flask, 87.3 mg of(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,40 mg of copper(II) acetate monohydrate, and 50 mL of ethyl acetate wereadded and mixed with stirring at an inner temperature of 50° C. for 30minutes. After being cooled to room temperature, 84.8 mg of 28 wt %sodium methylate/methanol solution was added thereto and the resultingmixture was kept under stirring further for 10 minutes. 50 mL of waterwas added to the reaction mixture and stirred. The resulting mixture wasallowed to stand and then an oil layer was separated. The oil layer wasdried over dehydrated sodium sulfate and then sodium sulfate wasfiltered and concentrated to obtain 99.4 mg of powder of[(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol]coppercomplex. Yield: 100%.

Example 8

To a 50 mL Schlenk tube purged with nitrogen, 9.94 mg of[(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol]coppercomplex obtained in Reference Example 1, 3.57 mg of triethoxyaluminumand 5 mL of ethyl acetate were added and stirred at room temperature for10 minutes to effect reaction and a solution containing optically activecopper catalyst composition was obtained. To the solution containingoptically active copper catalyst composition, 4 mg of phenylhydrazinewas added, and then 7.8 g of 2,5-dimethyl-2,4-hexadiene was addedthereto and the resulting mixture was cooled to an inner temperature of0° C. 5 mL of the ethyl acetate solution containing 1.14 g of ethyldiazoacetate was added dropwise thereto over 2 hours at the sametemperature. After adding dropwise, the resulting mixture was stirred atthe same temperature for 30 minutes to effect reaction and the reactionmixture containing optically active ethyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate wasobtained. The yield of optically active ethyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was 86%, andthe trans-isomer/cis-isomer ratio=57/43. The residual ratio of ethyldiazoacetate was 0.1%. Optical purity of the trans-isomer was 84% e.e.and that of the cis-isomer was 79% e.e.

Example 9

To a 50 mL Schlenk tube purged with nitrogen, 9.94 mg of[(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol]coppercomplex obtained in Reference Example 1, 3.57 mg of triethoxyaluminumand 5 mL of ethyl acetate were added and stirred at room temperature for10 minutes to effect reaction and a solution containing optically activecopper catalyst composition was obtained. To the solution containingoptically active copper catalyst composition, 4 mg of phenylhydrazinewas added, and then 7.8 g of 2,5-dimethyl-2,4-hexadiene was addedthereto and the resulting mixture was cooled to an inner temperature of20° C. 5 mL of the ethyl acetate solution containing 1.41 g oftert-butyl diazoacetate was added dropwise thereto over 2 hours at thesame temperature. After adding dropwise, the resulting mixture wasstirred at the same temperature for 30 minutes to effect reaction andthe reaction mixture containing optically active tert-butyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate wasobtained. The yield of optically active tert-butyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was 90%, andthe trans-isomer/cis-isomer ratio=77/23. The residual ratio of ethyldiazoacetate was 0.1%. Optical purity of the trans-isomer was 91% e.e.and that of the cis-isomer was 62% e.e.

Comparative Example 3

According to the same manner as that described in Example 9, opticallyactive tert-butyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was obtainedin a yield of 27% and the trans-isomer/cis-isomer ratio=79/21 exceptthat triethoxyaluminum was not used. The residual ratio of ethyldiazoacetate was 48%. Also, optical purity of the trans-isomer was 91%e.e. and that of the cis-isomer was 62% e.e.

Reference Example 2

In a 200 mL flask, 127 mg of(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol,40 mg of copper(II) acetate monohydrate, and 50 mL of ethyl acetate wereadded and mixed with stirring at an inner temperature of 50° C. for 30minutes. After being cooled to room temperature, 84.8 mg of 28 wt %sodium methylate/methanol solution was added thereto and the resultingmixture was kept under stirring further for 10 minutes. 50 mL of waterwas added to the reaction mixture and stirred. The resulting mixture wasallowed to stand and then an oil layer was separated. The oil layer wasdried over dehydrated sodium sulfate and then sodium sulfate wasfiltered and concentrated to obtain 139 mg of powder of[(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol]coppercomplex. Yield: 100%.

Example 10

To a 50 mL Schlenk tube purged with nitrogen, 6.94 mg of[(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol]coppercomplex obtained in Reference Example 2, 1.78 mg of triethoxyaluminumand 5 mL of ethyl acetate were added and stirred at room temperature for10 minutes to effect reaction and a solution containing optically activecopper catalyst composition was obtained. To the solution containingoptically active copper catalyst composition obtained, 2 mg ofphenylhydrazine was added, and then 7.7 g of 2,5-dimethyl-2,4-hexadienewas added thereto and the resulting mixture was cooled to an innertemperature of 0° C. 5 mL of the ethyl acetate solution containing 1.14g of ethyl diazoacetate was added dropwise thereto over 2 hours at thesame temperature. After adding dropwise, the resulting mixture wasstirred at the same temperature for 30 minutes to effect reaction andthe reaction mixture containing optically active ethyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate wasobtained. The yield of optically active ethyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was 83%, andthe trans-isomer/cis-isomer ratio=49/51. The residual ratio of ethyldiazoacetate was 0.1%. Optical purity of the trans-isomer was 83% e.e.and that of the cis-isomer was 68% e.e.

Comparative Example 4

According to the same manner as that described in Example 10, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 56% and the trans-isomer/cis-isomerratio=50/50 except that triethoxyaluminum was not used. The residualratio of ethyl diazoacetate was 6%. Optical purity of the trans-isomerwas 82% e.e. and that of the cis-isomer was 67% e.e.

Reference Example 3

In a 200 mL flask, 89.9 mg of(R)-N-(5-methoxycarbonylsalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol,40 mg of copper(II) acetate monohydrate, and 50 mL of ethyl acetate wereadded and mixed with stirring at an inner temperature of 50° C. for 30minutes. After being cooled to room temperature, 84.8 mg of 28 wt %sodium methylate/methanol solution was added thereto and the resultingmixture was kept under stirring further for 10 minutes. 50 mL of waterwas added to the reaction mixture and stirred. The resulting mixture wasallowed to stand and then an oil layer was separated. The oil layer wasdried over dehydrated sodium sulfate and then sodium sulfate wasfiltered and concentrated to obtain 102 mg of powder of[(R)-N-(5-methoxycarbonylsalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol]coppercomplex. Yield: 100%.

Example 11

According to the same manner as that described in Example 10, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 72% and the trans-isomer/cis-isomerratio=57/43 except that 10.2 mg of[(R)-N-(5-methoxycarbonylsalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol]coppercomplex obtained in Reference Example 3 was used in place of 6.94 mg of[(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol]coppercomplex obtained in Reference Example 2. The residual ratio of ethyldiazoacetate was 11%. Optical purity of the trans-isomer was 85% e.e.and that of the cis-isomer was 80% e.e.

Comparative Example 5

According to the same manner as that described in Example 11, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 35% and the trans-isomer/cis-isomerratio=58/42 except that triethoxyaluminum was not used. The residualratio of ethyl diazoacetate was 45%. Optical purity of the trans-isomerwas 84% e.e. and that of the cis-isomer was 79% e.e.

Reference Example 4

According to the same manner as that described in Reference Example 3,95.6 mg of powder of[(R)-N-(5-cyanosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol]coppercomplex was obtained except that 83.3 mg of(R)-N-(5-cyanosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanolwas used in place of 89.9 mg of(R)-N-(5-methoxycarbonylsalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol.Yield: 100%.

Example 12

According to the same manner as that described in Example 10, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 52% and the trans-isomer/cis-isomerratio=57/43 except that 9.56 mg of[(R)-N-(5-cyanosalicylidene)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol]coppercomplex obtained in Reference Example 4 was used in place of 6.94 mg of[(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol]coppercomplex obtained in Reference Example 2. The residual ratio of ethyldiazoacetate was 26%. Optical purity of the trans-isomer was 85% e.e.and that of the cis-isomer was 80% e.e.

Comparative Example 6

According to the same manner as that described in Example 12, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 29% and the trans-isomer/cis-isomerratio=58/42 except that triethoxyaluminum was not used. The residualratio of ethyl diazoacetate was 59%. Optical purity of the trans-isomerwas 84% e.e. and that of the cis-isomer was 79% e.e.

Comparative Example 7

According to the same manner as that described in Example 10, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 6% and the trans-isomer/cis-isomerratio=59/41 except that 22.65 mg of[(R)-N-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-1-propanol]coppercomplex was used in place of 6.94 mg of[(R)-N-(5-nitrosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-n-butoxyphenyl)-1-propanol]coppercomplex obtained in Reference Example 2. The yield of dimerizationby-product was 6% and the residual ratio of ethyl diazoacetate was 84%.Optical purity of the trans-isomer was 50% e.e. and that of thecis-isomer was 49% e.e.

Comparative Example 8

According to the same manner as that described in Comparative Example 7,optically active ethyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was obtainedin a yield of 5% and the trans-isomer/cis-isomer ratio=59/41 except thattriethoxyaluminum was not used. The yield of dimerization by-product was10% and the residual ratio of ethyl diazoacetate was 84%. Optical purityof the trans-isomer was 48% e.e. and that of the cis-isomer was 47% e.e.

Example 13

According to the same manner as that described in Example 8, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 85% and the trans-isomer/cis-isomerratio=57/43 except that 0.84 mg of lithium methoxide was used in placeof 3.57 mg of triethoxyaluminum. The residual ratio of ethyldiazoacetate was 0.1%. Optical purity of the trans-isomer was 85% e.e.and that of the cis-isomer was 78% e.e.

Example 14

According to the same manner as that described in Example 8, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 86% and the trans-isomer/cis-isomerratio=58/42 except that 0.53 mg of lithium hydroxide was used in placeof 3.57 mg of triethoxyaluminum. The residual ratio of ethyldiazoacetate was 0.1%. Optical purity of the trans-isomer was 81% e.e.and that of the cis-isomer was 75% e.e.

Example 15

According to the same manner as that described in Example 8, opticallyactive ethyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylatewas obtained in a yield of 82% and the trans-isomer/cis-isomerratio=58/42 except that 0.57 mg of lithium fluoride was used in place of3.57 mg of triethoxyaluminum. The residual ratio of ethyl diazoacetatewas 0.1%. Optical purity of the trans-isomer was 81% e.e. and that ofthe cis-isomer was 76% e.e.

INDUSTRIAL APPLICABILITY

According to the present invention, diazotization reaction catalystwhich exhibits good activity can be obtained. The catalyst exhibits goodactivity, for example, at low reaction temperature. It is possible toproduce an optically active cyclopropane compound easily by using thecatalyst.

1. An optically active copper catalyst composition comprising (a) anoptically active salicylideneaminoalcohol represented by the formula(1):

wherein R¹ and R² are the same or different, and independently representa substituted or unsubstituted lower alkyl group, a substituted orunsubstituted aralkyl group, or a substituted or unsubstituted arylgroup; X¹ and X² are the same or different, and independently representa hydrogen atom, a lower alkoxy group, a nitro group, a loweralkoxycarbonyl group, a cyano group or a halogen atom; and * representsan asymmetric center, provided that both of X¹ and X² don't representhydrogen atoms, (b) a monovalent or divalent copper compound, and (c-1)a lithium compound or (c-2) a compound selected from aluminum compoundshaving Lewis acidity, titanium compounds having Lewis acidity, boroncompounds having Lewis acidity, zirconium compounds having Lewis acidityand hafnium compounds having Lewis acidity.
 2. An organic solventsolution or a slurry containing the optically active copper catalystcomposition according to claim 1, which is obtained by contacting theoptically active salicylideneaminoalcohol represented by the formula(1), the monovalent or divalent copper compound, and the lithiumcompound or the compound selected from c-2) in an organic solvent. 3.The optically active copper catalyst composition, the organic solventsolution or the slurry containing the composition according to claim 2,which is obtained by contacting the optically activesalicylideneaminoalcohol represented by the formula (1), the monovalentor divalent copper compound, and the lithium compound.
 4. The opticallyactive copper catalyst composition or the organic solvent solution orthe slurry containing the composition according to claim 2, which isobtained by contacting the optically active salicylideneaminoalcoholrepresented by the formula (1), the monovalent or divalent coppercompound, and the Lewis acid.
 5. The optically active copper catalystcomposition according to claim 1, wherein the lithium compound islithium salt, lithium alkoxide or lithium hydroxide.
 6. The opticallyactive copper catalyst composition according to claim 1, whereinaluminum compounds having Lewis acidity is trihaloaluminum,trialkylaluminum, trialkoxyaluminum, triaryloxyaluminum, ortris(pentafluorophenyl)aluminum, titanium compounds having Lewis acidityis tetrahalotitanium or tetraalkoxytitanium, boron compounds havingLewis acidity is boron trifluoride diethyl etherate, triethylborane,triphenylborane, or tris(pentafluorophenyl)borane, zirconium compoundshaving Lewis acidity is zirconium halide (IV) or the complex, ortetraalkoxyzirconium, and hafnium compounds having Lewis acidity ishafnium halide (IV) or the complex.
 7. The optically active coppercatalyst composition according to claim 6, wherein aluminum compoundshaving Lewis acidity is trimethylaluminum, triethylaluminum,triisobutylaluminum, triethoxyaluminum, or triphenoxyaluminum, titaniumcompounds having Lewis acidity is titanium tetrahalide,tetraisopropoxytitanium or tetra(n-butoxy)titanium, zirconium compoundshaving Lewis acidity is zirconium tetrachloride, zirconium tetrachloridetetrahydrofuran complex or tetra(n-butoxy)zirconium, and hafniumcompounds having Lewis acidity is hafnium tetrachloride or hafniumtetrachloride tetrahydrofuran complex.
 8. The optically active coppercatalyst composition according to claim 1 or 2, wherein the compoundselected from (c-2) is methoxylithium, triethoxyaluminum,tris(pentafluorophenyl)aluminum, tetraisopropoxytitanium ortris(pentafluorophenyl)borane.
 9. The optically active copper catalystcomplex composition according to claim 1, wherein the amount of thecompound selected from (c-2) used is 0.3 to 5 moles per 1 mole of themonovalent or divalent copper compound.
 10. The organic solvent solutionor the slurry containing the optically active copper catalystcomposition according to claim 2, wherein the amount of the compoundselected from (c-2) used is 0.3 to 5 moles per 1 mole of the monovalentor divalent copper compound.
 11. The optically active copper catalystcomposition, or the organic solvent solution or the slurry containingthe composition according to claim 1 or 2, wherein the monovalent ordivalent copper compound is a C2-5 copper organic carboxylate, copperhalide, copper methanesulfonate, copper trifluoromethanesulfonate,copper carbonate or copper hydroxide.
 12. A process for producing anoptically active cyclopropane compound represented by the formula (4):

wherein R³, R⁴, R⁵ and R⁶ are the same or different, and independentlyrepresent a hydrogen atom, an alkyl group which may be substituted withone or more halogen atom, an alkenyl group which may be substituted withone or more halogen atom, an aryl group or an aralkyl group; providedthat, when R³ and R⁵ are the same, R³ and R⁴ are different from eachother; and R⁷ represents a C1-6 alkyl group, which comprises reacting aprochiral olefin represented by the formula (2):

wherein R³, R⁴, R⁵ and R⁶ are as defined above, with a diazoacetic acidester represented by the formula (3):N₂CHCO₂R⁷  (3) wherein R⁷ is as described above, in the presence of theoptically active copper catalyst composition according to any one ofclaim 1 to
 6. 13. The process for producing an optically activecyclopropane compound according to claim 12, wherein the prochiralolefin (2) is 2,5-dimethyl-2,4-hexadiene.